912 resultados para non-process elements


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La majoria de les fallades en elements estructurals són degudes a càrrega per fatiga. En conseqüència, la fatiga mecànica és un factor clau per al disseny d'elements mecànics. En el cas de materials compòsits laminats, el procés de fallada per fatiga inclou diferents mecanismes de dany que resulten en la degradació del material. Un dels mecanismes de dany més importants és la delaminació entre capes del laminat. En el cas de components aeronàutics, les plaques de composit estan exposades a impactes i les delaminacions apareixen facilment en un laminat després d'un impacte. Molts components fets de compòsit tenen formes corbes, superposició de capes i capes amb diferents orientacions que fan que la delaminació es propagui en un mode mixt que depen de la grandària de la delaminació. És a dir, les delaminacions generalment es propaguen en mode mixt variable. És per això que és important desenvolupar nous mètodes per caracteritzar el creixement subcrític en mode mixt per fatiga de les delaminacions. El principal objectiu d'aquest treball és la caracterització del creixement en mode mixt variable de les delaminacions en compòsits laminats per efecte de càrregues a fatiga. Amb aquest fi, es proposa un nou model per al creixement per fatiga de la delaminació en mode mixt. Contràriament als models ja existents, el model que es proposa es formula d'acord a la variació no-monotònica dels paràmetres de propagació amb el mode mixt observada en diferents resultats experimentals. A més, es du a terme un anàlisi de l'assaig mixed-mode end load split (MMELS), la característica més important del qual és la variació del mode mixt a mesura que la delaminació creix. Per a aquest anàlisi, es tenen em compte dos mètodes teòrics presents en la literatura. No obstant, les expressions resultants per l'assaig MMELS no són equivalents i les diferències entre els dos mètodes poden ser importants, fins a 50 vegades. Per aquest motiu, en aquest treball es porta a terme un anàlisi alternatiu més acurat del MMELS per tal d'establir una comparació. Aquest anàlisi alternatiu es basa en el mètode dels elements finits i virtual crack closure technique (VCCT). D'aquest anàlisi en resulten importants aspectes a considerar per a la bona caracterització de materials utilitzant l'assaig MMELS. Durant l'estudi s'ha dissenyat i construït un utillatge per l'assaig MMELS. Per a la caracterització experimental de la propagació per fatiga de delaminacions en mode mixt variable s'utilitzen diferents provetes de laminats carboni/epoxy essencialment unidireccionals. També es du a terme un anàlisi fractogràfic d'algunes de les superfícies de fractura per delaminació. Els resultats experimentals són comparats amb les prediccions del model proposat per la propagació per fatiga d'esquerdes interlaminars.

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Aquesta tesi estudia algunes de les transformacions agràries enregistrades en un àmbit comarcal (la comarca catalana del Baix Empordà) entre mitjan segle XIX i mitjan segle XX. EI fil conductor és la distribució de la propietat del sol agrícola. Però per a la seva comprensió es considera necessari integrar moltes altres variables. EI treball també es proposa assajar alguns procediments metodològics poc habituals en l'anàlisi de la distribució de la propietat del sòl agrícola i la seva evolució en època contemporània. Com a hipòtesi central, es sosté que, al Baix Empordà i al llarg del període comprès entre 1850 i 1940, els canvis que varen produir-se en l'estructura de la propietat i, també, en I'estructura social rural, varen apuntar genèricament a favor dels grups pagesos. En particular, es sosté : ( I) Que la situació de partida (de mitjan segle XIX) ja es caracteritzava per un notable pes de la petita propietat pagesa sobre I'estructura de la propietat agrícola i sobre el conjunt del sistema agrari. (2) Que, amb posterioritat a la crisi agrària finisecular, els problemes de rendibilitat de la producció agrària i l'erosió soferta per alguns mecanismes d'extracció de renda varen tendir a allunyar els sectors rendistes que tradicionalment havien exercit la seva hegemonia -econòmica i social- en la societat rural. (3) I, finalment, que al llarg del període va produir-se un avenç de la propietat pagesa com a conseqüència del fet que una porció significativa de famílies pageses aconseguissin ampliar el seu patrimoni territorial a través de compres realitzades en el mercat de terres, alhora que un nombre significatiu de vells grans patrimonis es fraccionava i desfeia. La magnitud d'aquests canvis va ser moderada i no va pas estar exempta d'ambigüitats, però posa de relleu la capacitat de resistència i adequació de l'explotació pagesa a les condicions d'un capitalisme evolvent, malgrat els pronòstics en sentit contrari de molts teòrics. La tesi està articulada en dues parts. En la primera es duu a terme una descripció detallada de les característiques del sistema agrari baixempordanès de mitjan segle XIX amb l'objectiu final de determinar el significat econòmic de les terres posseïdes per cada patrimoni familiar (més enllà de la simple consideració de les superfícies). EI primer pas consisteix en l'anàlisi dels usos del sòl, dels conreus principals i la seva ordenació en rotacions, dels rendiments físics, de les practiques de reposició de la fertilitat i de la dotació ramadera. A continuació es descriuen les tècniques i el procés de treball agrari amb l'objectiu de formular un model d'organització del treball agrícola que permeti mesurar les exigències en treball d'aquesta activitat. Es conclou que, des de la perspectiva de l'ocupació i de la demanda de treball generades pel sistema agrari, les localitats rurals es caracteritzaven per un fort excedent de mà d'obra en relació a les demandes laborals dels conreus tant des d'una perspectiva macroeconòmica com microeconòmica. EI tercer capítol es centra en l'avaluació de les necessitats de consum i reproducció de les UFP. Les estimacions realitzades permeten proposar un model flexible, que és contrastat amb els ingressos potencialment obtenibles per cada patrimoni. S'arriba a la conclusió que només una ínfima part de la població arribava a obtenir, amb l'explotació directa del seu patrimoni, l'ingrés necessari per a la seva reproducció econòmica simple. Paral·lelament però, es posa de relleu la importància econòmica i social dels petits patrimonis pagesos. S'estima que entorn una mitjana del 45% del sòl agrícola estava posseït per aquest segment de propietaris i, en el quart capítol, s'estudien les implicacions d'aquest fet. EI retrat de la situació de partida finalitza amb l'estudi dels règims de no-propietat predominants a la comarca. En la segona part, aquesta visió estàtica deixa pas a una anàlisi dinàmica. A mitjan segle XIX, al Baix Empordà, s'estava arribant a la fi d'una llarga etapa expansiva iniciada una centúria abans. Els primers signes d'esgotament varen ser la intensa pèrdua de població rural entre 1860 i 1880, la paralització de l'expansió dels conreus i el fort desenvolupament de la industria surera, eix del nou motor econòmic comarcal. Amb posterioritat a 1860 els canvis en l'estructura distributiva de la propietat varen tendir a apuntar cap a la consolidació de la propietat pagesa. Es va produir un procés de transferència de terres des dels sectors rendistes cap a sectors pagesos que va realitzar-se a través de compravendes en el mercat de la terra més que a través d'establiments i subestabliments emfitèutics. Va tenir com a conseqüència última el retrocés dels vells patrimonis rendistes, que, en general, no varen ser substituïts per l'aparició de nous grans patrimonis, com havia pogut passar fins aleshores. Paral·lelament, un bon nombre d'unitats familiars rurals també varen anar abandonant el camp i les seves propietats, produint-se una altra línia de transferència de terres entre sectors pagesos. La depreciació sostinguda dels preus agrícoles, la caiguda de la renda agrària, la superior rendibilitat de les inversions en valors mobiliaris i la incidència d'una creixent conflictivitat agrària són els factors que es destaquen per explicar la reculada dels grans patrimonis territorials. Des de la perspectiva pagesa es proposen tres elements explicatius per interpretar el procés d'acumulació patrimonial observat en un determinat segment de població: (1) el manteniment d'estratègies de producció per a l'autoconsum (un aspecte sempre polèmic i de difícil demostració); (2) l'existència d'un flux important d'ingressos salarials i extra-agrícoles en la composició de l'ingrés familiar pagès; i (3) el canvi en les orientacions tècniques i productives de les explotacions pageses. La combinació dels tres, alhora que hauria limitat els efectes directes dels moviments dels preus agraris, hauria possibilitat l'estratègia acumulativa observada.

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Este trabalho de investigação consiste num estudo empírico sobre uma nova ciência - a Biblioterapia, e a situação mais específica, a sua aplicação em contexto prisional. Para alcançar este objetivo formulámos a seguinte hipótese: “o livro exerce sobre as pessoas em geral e, de uma forma mais particular, sobre indivíduos em contexto de detenção institucional uma função terapêutica”. A metodologia adotada para esta investigação assenta essencialmente em fontes documentais textuais e digitais, sobre autores especialistas na matéria, que de uma forma mais precisa se identificam e citam especificamente no capítulo referente à revisão da literatura. Para atingir o nosso propósito começámos por definir os conceitos de leitura, de leitura terapêutica, de fenomenologia da linguagem, de terapia e de diálogo assim como procurámos saber quais os fundamentos filosóficos e os componentes biblioterapêuticos, público-alvo e áreas com maiores potencialidades de aplicação, benefícios e limitações que norteiam à aplicação da Biblioterapia, nomeadamente, para fins de desenvolvimento pessoal e de alterações comportamentais. Fez-se igualmente uma análise da evolução do conceito, desde Aristóteles até aos nossos dias. Só com o conhecimento efetivo desta realidade seria possível prosseguir o nosso objeto de estudo. Entendemos ainda ser importante perceber qual é a situação da leitura em Portugal e as políticas desenvolvidas nesta área pelo Estado, para promover a leitura junto dos estudantes e da população em geral. Apenas assente nestas duas realidades que se entrecruzam, no processo de leitor/livro é possível identificar e relacionar esta problemática em estudo. Constatamos a existência de dois tipos de Biblioterapia, a Biblioterapia-arte e a Biblioterapia-ciência, identificando algumas das suas características, principalmente o que as aproxima e o que as separa. Apresentamos um exemplo de uma área reconhecidamente bem sucedida na aplicação da Biblioterapia não-clínica, em instituições prisionais, efetuando uma abordagem às questões mais pertinentes neste campo: os seus aspetos institucionais, os psicossociais e os de reinserção social. Considerámos ainda as recomendações da IFLA para este setor populacional – Guidelines for Library Services to Prisoners. Ao longo do trabalho e de uma forma transversal realçamos as interrelações biblioterapêuticas entre pacientes, bibliotecários e outros intervenientes no processo biblioterapêutico, tais como médicos e orientadores de leitura. Finalizamos o trabalho concluindo que a prática de leitura de temas específicos, em qualquer campo de atuação e sob orientação de um elemento profissional com conhecimentos aprofundados tanto em relação às personalidades e problemas dos destinatários como aos materiais que tem à sua disposição – o livro, em sentido lato - pode efetivamente desencadear benefícios terapêuticos nos leitores.

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Most parameterizations for precipitating convection in use today are bulk schemes, in which an ensemble of cumulus elements with different properties is modelled as a single, representative entraining-detraining plume. We review the underpinning mathematical model for such parameterizations, in particular by comparing it with spectral models in which elements are not combined into the representative plume. The chief merit of a bulk model is that the representative plume can be described by an equation set with the same structure as that which describes each element in a spectral model. The equivalence relies on an ansatz for detrained condensate introduced by Yanai et al. (1973) and on a simplified microphysics. There are also conceptual differences in the closure of bulk and spectral parameterizations. In particular, we show that the convective quasi-equilibrium closure of Arakawa and Schubert (1974) for spectral parameterizations cannot be carried over to a bulk parameterization in a straightforward way. Quasi-equilibrium of the cloud work function assumes a timescale separation between a slow forcing process and a rapid convective response. But, for the natural bulk analogue to the cloud-work function (the dilute CAPE), the relevant forcing is characterised by a different timescale, and so its quasi-equilibrium entails a different physical constraint. Closures of bulk parameterization that use the non-entraining parcel value of CAPE do not suffer from this timescale issue. However, the Yanai et al. (1973) ansatz must be invoked as a necessary ingredient of those closures.

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In the UK, the recycling of sewage sludge to land is expected to double by 2006 but the security of this route is threatened by environmental concerns and health scares. Strategic investment is needed to ensure sustainable and secure sludge recycling outlets. At present, the security of this landbank for sludge recycling is determined by legislation relating to nutrient rather than potentially toxic elements (PTEs) applications to land - especially the environmental risk linked to soil phosphorus (P) saturation. We believe that not all land has an equal risk of contributing nutrients derived from applications to land to receiving waters. We are currently investigating whether it is possible to minimise nutrient loss by applying sludge to land outside Critical Source Areas (CSAs) regardless of soil P Index status. Research is underway to develop a predictive and spatially-sensitive, semi-distributed model of critical thresholds for sludge application that goes beyond traditional 'end-of-pipe" or "edge-of-field" modelling, to include hydrological flow paths and delivery mechanisms to receiving waters from non-point sources at the catchment scale.

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Plant uptake of organic chemicals is an important process when considering the risks associated with land contamination, the role of vegetation in the global cycling of persistent organic pollutants, and the potential for industrial discharges to contaminate the food chain. There have been some significant advances in our understanding of the processes of plant uptake of organic chemicals in recent years; most notably there is now a better understanding of the air to plant transfer pathway, which may be significant for a number of industrial chemicals. This review identifies the key processes involved in the plant uptake of organic chemicals including those for which there is currently little information, e.g., plant lipid content and plant metabolism. One of the principal findings is that although a number of predictive models exist using established relationships, these require further validation if they are to be considered sufficiently robust for the purposes of contaminated land risk assessment or for prediction of the global cycling of persistent organic pollutants. Finally, a number of processes are identified which should be the focus of future research

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This paper explores the provision of homes for less wealthy households in rural England. By allowing 'exceptions' to UK planning law to provide low-income housing for local residents, the national government seeks to secure dwellings for the less wealthy and so sustain socially mixed rural villages. This paper explores how the production of homes through the exception policy is not conducive to the construction of many new houses. The particular emphasis in the paper is on how responsible agents are discouraged from being more active in erecting new village homes for low-income households. Empirically, the paper draws on documents, interviews and a social survey in the counties of Bedfordshire, Cambridgeshire and Norfolk to investigate the process of delivering rural exception homes. It is concluded that, despite Government assertions that a socially mixed countryside is desirable, the decision-making criteria that dominate the worldviews of agents in social housing provision work against this outcome. (c) 2005 Elsevier Ltd. All rights reserved.

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A semi-distributed model, INCA, has been developed to determine the fate and distribution of nutrients in terrestrial and aquatic systems. The model simulates nitrogen and phosphorus processes in soils, groundwaters and river systems and can be applied in a semi-distributed manner at a range of scales. In this study, the model has been applied at field to sub-catchment to whole catchment scale to evaluate the behaviour of biosolid-derived losses of P in agricultural systems. It is shown that process-based models such as INCA, applied at a wide range of scales, reproduce field and catchment behaviour satisfactorily. The INCA model can also be used to generate generic information for risk assessment. By adjusting three key variables: biosolid application rates, the hydrological connectivity of the catchment and the initial P-status of the soils within the model, a matrix of P loss rates can be generated to evaluate the behaviour of the model and, hence, of the catchment system. The results, which indicate the sensitivity of the catchment to flow paths, to application rates and to initial soil conditions, have been incorporated into a Nutrient Export Risk Matrix (NERM).

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We give a non-commutative generalization of classical symbolic coding in the presence of a synchronizing word. This is done by a scattering theoretical approach. Classically, the existence of a synchronizing word turns out to be equivalent to asymptotic completeness of the corresponding Markov process. A criterion for asymptotic completeness in general is provided by the regularity of an associated extended transition operator. Commutative and non-commutative examples are analysed.

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Preface. Iron is considered to be a minor element employed, in a variety of forms, by nearly all living organisms. In some cases, it is utilised in large quantities, for instance for the formation of magnetosomes within magnetotactic bacteria or during use of iron as a respiratory donor or acceptor by iron oxidising or reducing bacteria. However, in most cases the role of iron is restricted to its use as a cofactor or prosthetic group assisting the biological activity of many different types of protein. The key metabolic processes that are dependent on iron as a cofactor are numerous; they include respiration, light harvesting, nitrogen fixation, the Krebs cycle, redox stress resistance, amino acid synthesis and oxygen transport. Indeed, it is clear that Life in its current form would be impossible in the absence of iron. One of the main reasons for the reliance of Life upon this metal is the ability of iron to exist in multiple redox states, in particular the relatively stable ferrous (Fe2+) and ferric (Fe3+) forms. The availability of these stable oxidation states allows iron to engage in redox reactions over a wide range of midpoint potentials, depending on the coordination environment, making it an extremely adaptable mediator of electron exchange processes. Iron is also one of the most common elements within the Earth’s crust (5% abundance) and thus is considered to have been readily available when Life evolved on our early, anaerobic planet. However, as oxygen accumulated (the ‘Great oxidation event’) within the atmosphere some 2.4 billion years ago, and as the oceans became less acidic, the iron within primordial oceans was converted from its soluble reduced form to its weakly-soluble oxidised ferric form, which precipitated (~1.8 billion years ago) to form the ‘banded iron formations’ (BIFs) observed today in Precambrian sedimentary rocks around the world. These BIFs provide a geological record marking a transition point away from the ancient anaerobic world towards modern aerobic Earth. They also indicate a period over which the bio-availability of iron shifted from abundance to limitation, a condition that extends to the modern day. Thus, it is considered likely that the vast majority of extant organisms face the common problem of securing sufficient iron from their environment – a problem that Life on Earth has had to cope with for some 2 billion years. This struggle for iron is exemplified by the competition for this metal amongst co-habiting microorganisms who resort to stealing (pirating) each others iron supplies! The reliance of micro-organisms upon iron can be disadvantageous to them, and to our innate immune system it represents a chink in the microbial armour, offering an opportunity that can be exploited to ward off pathogenic invaders. In order to infect body tissues and cause disease, pathogens must secure all their iron from the host. To fight such infections, the host specifically withdraws available iron through the action of various iron depleting processes (e.g. the release of lactoferrin and lipocalin-2) – this represents an important strategy in our defence against disease. However, pathogens are frequently able to deploy iron acquisition systems that target host iron sources such as transferrin, lactoferrin and hemoproteins, and thus counteract the iron-withdrawal approaches of the host. Inactivation of such host-targeting iron-uptake systems often attenuates the pathogenicity of the invading microbe, illustrating the importance of ‘the battle for iron’ in the infection process. The role of iron sequestration systems in facilitating microbial infections has been a major driving force in research aimed at unravelling the complexities of microbial iron transport processes. But also, the intricacy of such systems offers a challenge that stimulates the curiosity. One such challenge is to understand how balanced levels of free iron within the cytosol are achieved in a way that avoids toxicity whilst providing sufficient levels for metabolic purposes – this is a requirement that all organisms have to meet. Although the systems involved in achieving this balance can be highly variable amongst different microorganisms, the overall strategy is common. On a coarse level, the homeostatic control of cellular iron is maintained through strict control of the uptake, storage and utilisation of available iron, and is co-ordinated by integrated iron-regulatory networks. However, much yet remains to be discovered concerning the fine details of these different iron regulatory processes. As already indicated, perhaps the most difficult task in maintaining iron homeostasis is simply the procurement of sufficient iron from external sources. The importance of this problem is demonstrated by the plethora of distinct iron transporters often found within a single bacterium, each targeting different forms (complex or redox state) of iron or a different environmental condition. Thus, microbes devote considerable cellular resource to securing iron from their surroundings, reflecting how successful acquisition of iron can be crucial in the competition for survival. The aim of this book is provide the reader with an overview of iron transport processes within a range of microorganisms and to provide an indication of how microbial iron levels are controlled. This aim is promoted through the inclusion of expert reviews on several well studied examples that illustrate the current state of play concerning our comprehension of how iron is translocated into the bacterial (or fungal) cell and how iron homeostasis is controlled within microbes. The first two chapters (1-2) consider the general properties of microbial iron-chelating compounds (known as ‘siderophores’), and the mechanisms used by bacteria to acquire haem and utilise it as an iron source. The following twelve chapters (3-14) focus on specific types of microorganism that are of key interest, covering both an array of pathogens for humans, animals and plants (e.g. species of Bordetella, Shigella, , Erwinia, Vibrio, Aeromonas, Francisella, Campylobacter and Staphylococci, and EHEC) as well as a number of prominent non-pathogens (e.g. the rhizobia, E. coli K-12, Bacteroides spp., cyanobacteria, Bacillus spp. and yeasts). The chapters relay the common themes in microbial iron uptake approaches (e.g. the use of siderophores, TonB-dependent transporters, and ABC transport systems), but also highlight many distinctions (such as use of different types iron regulator and the impact of the presence/absence of a cell wall) in the strategies employed. We hope that those both within and outside the field will find this book useful, stimulating and interesting. We intend that it will provide a source for reference that will assist relevant researchers and provide an entry point for those initiating their studies within this subject. Finally, it is important that we acknowledge and thank wholeheartedly the many contributors who have provided the 14 excellent chapters from which this book is composed. Without their considerable efforts, this book, and the understanding that it relays, would not have been possible. Simon C Andrews and Pierre Cornelis

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Planning is a vital element of project management but it is still not recognized as a process variable. Its objective should be to outperform the initially defined processes, and foresee and overcome possible undesirable events. Detailed task-level master planning is unrealistic since one cannot accurately predict all the requirements and obstacles before work has even started. The process planning methodology (PPM) has thus been developed in order to overcome common problems of the overwhelming project complexity. The essential elements of the PPM are the process planning group (PPG), including a control team that dynamically links the production/site and management, and the planning algorithm embodied within two continuous-improvement loops. The methodology was tested on a factory project in Slovenia and in four successive projects of a similar nature. In addition to a number of improvement ideas and enhanced communication, the applied PPM resulted in 32% higher total productivity, 6% total savings and created a synergistic project environment.

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Tick-borne encephalitis virus (TBEV) causes human epidemics across Eurasia. Clinical manifestations range from inapparent infections and fevers to fatal encephalitis but the factors that determine disease severity are currently undefined. TBEV is characteristically a hemagglutinating (HA) virus; the ability to agglutinate erythrocytes tentatively reflects virion receptor/fusion activity. However, for the past few years many atypical HA-deficient strains have been isolated from patients and also from the natural European host tick, Ixodes persulcatus. By analysing the sequences of HA-deficient strains we have identified 3 unique amino acid substitutions (D67G, E122G or D277A) in the envelope protein, each of which increases the net charge and hydrophobicity of the virion surface. Therefore, we genetically engineered virus mutants each containing one of these 3 substitutions; they all exhibited HA-deficiency. Unexpectedly, each genetically modified non-HA virus demonstrated increased TBEV reproduction in feeding Ixodes ricinus, not the recognised tick host for these strains. Moreover, virus transmission efficiency between infected and uninfected ticks co-feeding on mice was also intensified by each substitution. Retrospectively, the mutation D67G was identified in viruses isolated from patients with encephalitis. We propose that the emergence of atypical Siberian HA-deficient TBEV strains in Europe is linked to their molecular adaptation to local ticks. This process appears to be driven by the selection of single mutations that change the virion surface thus enhancing receptor/fusion function essential for TBEV entry into the unfamiliar tick species. As the consequence of this adaptive mutagenesis, some of these mutations also appear to enhance the ability of TBEV to cross the human blood-brain barrier, a likely explanation for fatal encephalitis. Future research will reveal if these emerging Siberian TBEV strains continue to disperse westwards across Europe by adaptation to the indigenous tick species and if they are associated with severe forms of TBE.

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Avian genomes are small and streamlined compared with those of other amniotes by virtue of having fewer repetitive elements and less non-coding DNA(1,2). This condition has been suggested to represent a key adaptation for flight in birds, by reducing the metabolic costs associated with having large genome and cell sizes(3,4). However, the evolution of genome architecture in birds, or any other lineage, is difficult to study because genomic information is often absent for long-extinct relatives. Here we use a novel bayesian comparative method to show that bone-cell size correlates well with genome size in extant vertebrates, and hence use this relationship to estimate the genome sizes of 31 species of extinct dinosaur, including several species of extinct birds. Our results indicate that the small genomes typically associated with avian flight evolved in the saurischian dinosaur lineage between 230 and 250 million years ago, long before this lineage gave rise to the first birds. By comparison, ornithischian dinosaurs are inferred to have had much larger genomes, which were probably typical for ancestral Dinosauria. Using comparative genomic data, we estimate that genome-wide interspersed mobile elements, a class of repetitive DNA, comprised 5 - 12% of the total genome size in the saurischian dinosaur lineage, but was 7 - 19% of total genome size in ornithischian dinosaurs, suggesting that repetitive elements became less active in the saurischian lineage. These genomic characteristics should be added to the list of attributes previously considered avian but now thought to have arisen in non-avian dinosaurs, such as feathers(5), pulmonary innovations 6, and parental care and nesting

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Reactions of the 1: 2 condensate (L) of benzil dihydrazone and 2-acetylpyridine with Hg(ClO4)(2) center dot xH(2)O and HgI2 yield yellow [HgL2](ClO4)(2) (1) and HgLI2 (2), respectively. Homoleptic 1 is a 8-coordinate double helical complex with a Hg(II)N-8 core crystallising in the space group Pbca with cell dimensions: a = 16.2250(3), b = 20.9563(7), c = 31.9886(11) angstrom. Complex 2 is a 4-coordinate single helical complex having a Hg(II)N2I2 core crystallising in the space group P2(1)/n with cell dimensions a = 9.8011(3), b = 17.6736(6), c = 16.7123(6) angstrom and b = 95.760(3). In complex 1, the N-donor ligand L uses all of its binding sites to act as tetradentate. On the other hand, it acts as a bidentate N-donor ligand in 2 giving rise to a dangling part. From variable temperature H-1 NMR studies both the complexes are found to be stereochemically non-rigid in solution. In the case of 2, the solution process involves wrapping up of the dangling part of L around the metal. (C) 2008 Elsevier B.V. All rights reserved.

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Background: Cannabinoids from cannabis (Cannabis sativa) are anti-inflammatory and have inhibitory effects on the proliferation of a number of tumorigenic cell lines, some of which are mediated via cannabinoid receptors. Cannabinoid (CB) receptors are present in human skin and anandamide, an endogenous CB receptor ligand, inhibits epidermal keratinocyte differentiation. Psoriasis is an inflammatory disease also characterised in part by epidermal keratinocyte hyper-proliferation. Objective: We investigated the plant cannabinoids Delta-9 tetrahydrocannabinol, cannabidiol, cannabinol and cannabigerol for their ability to inhibit the proliferation of a hyper-proliferating human keratinocyte cell line and for any involvement of cannabinoid receptors. Methods: A keratinocyte proliferation assay was used to assess the effect of treatment with cannabinoids. Cell integrity and metabolic competence confirmed using lactate-dehydrogenase and adenosine tri-phosphate assays. To determine the involvement of the receptors, specific agonist and antagonist were used in conjunction with some phytocannabinoids. Western blot and RT-PCR analysis confirmed presence of CB1 and CB2 receptors. Results: The cannabinoids tested all inhibited keratinocyte proliferation in a concentration-dependent manner. The selective CB2 receptor agonists JWH015 and BML190 elicited only partial inhibition, the non-selective CB agonist HU210 produced a concentration-dependent response, the activity of theses agonists were not blocked by either C81 /C82 antagonists. Conclusion: The results indicate that while CB receptors may have a circumstantial role in keratinocyte proliferation, they do not contribute significantly to this process. Our results show that cannabinoids inhibit keratinocyte proliferation, and therefore support a potential role for cannabinoids in the treatment of psoriasis. (c) 2006 Japanese Society for Investigative Dermatology. Published by Elsevier Ireland Ltd. All rights reserved.